Nickel-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries

ABSTRACT

Positive electrode-active materials for use in lithium-ion and lithium-ion polymer batteries contain quaternary composite oxides of manganese, nickel, cobalt and aluminum where one of the four is present at levels of over 70 mol percent. The composite oxides can be lithiated to form positive electrode-active materials that are stable over at least ten charge/discharge cycles at voltage levels over 4.8 volts, and have capacities of over 200 mAh/g. Methods for producing the materials and electrochemical cells and batteries that include the materials are also provided.

CROSS REFERENCE TO RELATED PATENTS AND PATENT APPLICATIONS

The subject matter of the present invention is related to the co-pendingand commonly assigned United States patent application titled“Manganese-Rich Quaternary Metal Oxide Materials As Cathodes ForLithium-ion And Lithium-ion Polymer Batteries”, which was filed on thesame date as the present application. The present application claims thebenefit of priority from U.S. Provisional Patent Application Ser. No.60/173,911, filed on Dec. 29, 1999.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to rechargeable power sources for portableelectronic devices such as camcorders, cell phones, laptop computers andtoys, and more particularly to positive electrode-active materials forlithium, lithium-ion and lithium-ion polymer batteries and methods ofmaking and using such materials.

2. Description of the Related Art

Rapid technological developments in the electronics and computerindustry have created a large consumer market for a variety ofbatteries. Today, batteries are used to power almost every portableelectronic device, such as cell phones, laptop computers, camcorders,portable radios, cameras and toys. With the continuing miniaturizationin the electronic industry and in portable electronic devices, thedemand for lightweight, compact, and yet high-energy density batterieshas been steadily increasing. In addition, a need for more efficientutilization of the available energy resources as well asair-quality-control has generated an enormous interest in thedevelopment of advanced high energy density batteries for electricpowered vehicles. Furthermore, cost effectiveness, rechargeability, andbetter safety characteristics have been other factors driving thebattery market.

Lithium-ion and lithium-ion polymer batteries represent a new generationof lightweight, compact, and yet high-energy power sources. This isparticularly true for lithium-ion polymer cells since they can be madevery thin, and with great shape flexibility. Lithium-based batteries areattractive for energy storage because of lithium's high specificcapacity (3800 Ah/kg) and low electronegativity (0.97). These propertieslead to energy cells (“cells”) with high energy density and highvoltage. The materials that are used to produce lithium-based batteriesare also less toxic than the components of nickel cadmium or lead acidcells, and their disposal poses fewer environmental problems.

The commercial and military applications of lithium-based batteries dateback to the 1960's and 1970's. Primary lithium batteries (single use,lithium metal as anode) were commercialized in the 1970's. These werefollowed by the development of rechargeable secondary cells that alsoused lithium metal as anodes in the early 1980's.

Typically, a lithium cell has been made up of a lithium metal negativeelectrode (“anode”), a positive electrode (“cathode”), such as manganeseoxide (Mn₂O₄), and some type of an electrolyte that serves as an ionicpath for lithium ion between two electrodes. During discharge, lithiumions from the metallic anode pass through the electrolyte to theelectrochemical materials of the cathode whereupon they releaseelectrical energy to an external circuit.

Since their commercialization, primary lithium cells (that is, cellswhich are used as a power source for one application and then arediscarded) have been widely used in both commercial and militaryapplications, while most rechargeable secondary cells have beenstruggling on the market. Difficulties associated with secondary cellsstem from reactions of lithium metal with electrolytes and the changesin the lithium surface that occur after repetitive charge-dischargecycling. Furthermore, the high reactivity of the lithium metal presentsa fire and explosive hazard, which becomes a serious concern when use isconsidered in larger cells.

In addressing the issues associated with highly reactive andirreversible metallic lithium anodes, a more advanced and inherentlysafer approach, the so-called rocking chair or lithium-ion cell, wasadopted in the late 1970's and early 1980's. In this approach, a lithiummetal negative electrode is replaced by a lithium intercalation materialor compound, such as lithiated carbon or lithiated metal oxides, whileanother lithium intercalation material is used for the positiveelectrode, or cathode. The operation of such a system involves theshuttling of lithium ions back and forth between the two intercalationcompounds during charge/discharge cycles. The output voltage of thesetypes of rocking chair cells is determined by the difference between theelectrochemical potential of lithium within the two lithiumintercalating electrodes.

An insertion compound is a host into/from which a guest species may betopotactically and reversibly inserted/extracted over a finite range ofsolid solution. Once such example would be graphite, which is known toreversibly intercalate lithium-ions and has been used as an anodematerial in lithium-ion batteries. Further examples of such compoundsare lithium metal oxides, where the metal can be selected from a widerange of metals.

Research and commercial development concerning rocking chair batterieshas been extensive since the adoption of that product. The firstcommercial lithium-ion cell based on the carbon anode and LiCoO₂ wasmarketed by Sony Corporation in about 1990.

Positive electrodes (cathodes) are the most critical component in thelithium-ion and lithium-ion polymer batteries, as they determine thebattery performance attributes such as operating voltage, energydensity, and cycle life. For the purposes of this specification, theterm “operating voltage” shall mean that working voltage produced whenthe battery is fully operational. For the purposes of thisspecification, the term “energy density” shall mean the energy producedper unit volume and or weight. For the purposes of this specification,the term “cycle life” shall mean the number of cycles that the batterycan experience in its effective lifetime. In this regard, lithiuminsertion compounds as cathode materials for lithium-ion batteries havebeen extensively investigated in the past two decades. Theelectrochemical potential range of lithium insertion compounds (withrespect to the Li metal) for a wide variety of compounds has beenobtained and documented such as in Manthiram et al, JOM, 49:43 (1997).

Among the insertion compounds that have been evaluated, LiCoO₂, LiNiO₂,and LiMn₂O₄ have been found to be most attractive. The theoreticalcapacities of both LiNiO₂ and LiCoO₂ are about 275 Ah/kg. However (froma practical matter), only a fraction of the theoretical capacity can bereached. Compared to LiNiO₂ and LiCoO₂, LiMn₂O₄ gives a lowertheoretical capacity of 148 Ah/kg and typically no more than 120 Ah/kgcan be obtained. At present, most commercial lithium-ion batteries useLiCoO₂ as the cathode material, whereas LiNiO₂ and LiMn₂O₄ are much lesscommon.

The preference of LiCoO₂ in commercial cells stems from its bettercycleability over LiNiO₂ and LiMn₂O₄, despite the fact that LiCoO₂ isthe most expensive of the three compounds. The reversible capacity ofLiNiO₂ is limited by irreversible phase transition on firstdelithiation, in which more than 10% of initial capacity can be lost. Inaddition, the thermal stability of LiNiO₂ is not good at its delithiatedstate, which can lead to safety concerns because of gaseous oxygenrelease. LiMn₂O₄, on the other hand, experiences problems due to Mndissolution from electrodes into electrolyte solution at high dischargerate, Jahn-Teller effects at the end of the deep discharge, andparasitic phase formation during the charge/discharge cycles. Forfurther information in this regard see Thackeray, M., et al.,Electrochemical and Solid State Letters, 1:7-9 (1998).

Despite the tremendous effort employed in improving the performance ofeach type of insertion compound by different preparation procedures, thecharge/discharge properties of these compounds are still not sufficientto satisfy commercial requirements. At present, at least, a singlemetal-based cathode material cannot meet all of the performancerequirements of lithium-ion batteries. Accordingly, the recent trend inbattery development has been shifted to multi-metallic insertioncompounds that can take advantage of the attributes of each metalcomponent. See for example: Huang D. Advanced Battery Technology, p. 21,Nov. (1998).

For instance, in Cedar et al., Nature, 392:694 (1998), it has been shownthat part of the transition metal in a cathode material could bereplaced by other elements such as non-transition-metal ions, whilestill retaining electrochemical Li-activity at higher voltage. Thearticle suggested that oxygen atoms are playing an important role inpromoting the electron exchange and the cell voltage correlates withincreased oxygen participation. Cedar and coworkers apparently observedimproved cell voltage and better cycleability in Al-adopted bimetallicLi_(x)Al_(y)Co_(1−y)O₂ and Li_(x)Al_(y)Mn_(1−y)O₂ systems. See, also,Cedar et al., Computational Materials Science, 161:8 (1997), and Jang etal., Electrochemical and Solid State Letters, 13:1 (1998).

Furthermore, U.S. Pat. Nos. 5,370,948 to Hasegawa et al., 5,264,201, toDahn et al., 5,626,635 to Yamamura et al., as well as academicpublications by Zhong et al., in J. Electrochem. Soc., 144:205 (1997);Amine et al., in J. Power Sources, 68:604 (1997), Fey et al. in J.Electrochem. Soc., 141:2279 (1994); Sigala et al., in Solid StateIonics, 81:167 (1995)); and Ein-Eli et al., J. Electrochem. Soc.,145:1238 (1998), describe binary cathode materials. Liu et al., in J.Electrochem. Soc., 879:143 (1996), describe the production of compositeoxides of one or two metals by forming a polymeric resin throughoutwhich metal ions are distributed. They show that the resin ishomogeneous at an atomic level and can be calcined at temperatures thatare lower than normally used to yield composite oxides that have highsurface area and unique morphologies.

Ternary and quaternary cathode combinations have also been explored,albeit much less than binary systems. In this regard, U.S. Pat. Nos.5,783,333 and 5,795,558, to PolyStor Corporation (Dublin, Calif.) andJapan Storage Battery Co., Ltd. (Tokyo, Japan), respectively, as well asacademic publications by Ein-Eli et al. in J. Electrochem. Soc., 146:908(1999) and Gao et al., in Electrochem. & Solid State Letters, 1:117(1998), describe such systems.

U.S. Pat. Nos. 5,718,989 and 5,795,558 to Aoki et al., describe positiveelectrode-active materials for a lithium secondary battery and a methodof producing them. The cathode materials described include formulationssuch as LiNi_(1−x−y−z)Co_(x)Mn_(y)Al_(z)O₂, but cobalt content neverexceeds 25 mol percent, manganese content never exceeds 30 mol percent,and aluminum content never exceeds 15 mol percent of the combined Ni,Co, Mn and Al content. These materials appear to be produced by aprocess which does not start with a homogeneous solution of the fourmetals that make up the composite oxide. The process, therefore, wouldnot be expected to provide molecular level mixing of all four of themetals before calcination. Moreover, the method appears not to use lowcovalent Mn (II) salt as the source of manganese, and would, therefore,not be expected to provide efficient oxidation of the mixture at lowertemperatures, so as to avoid phase separation of the calcined compositeoxide material. Electrodes that are produced by the disclosed processwere apparently never tested by charging to over 4.1 volts, too low avoltage level to provide any indication of the performance of suchmaterials at higher voltage levels, i.e., above about 4.6 volts.

U.S Pat. Nos. 5,783,333 and 6,007,947 to Mayer disclose the formation ofternary material formulated as Li_(x)Ni_(y)Co_(x)M_(z)O₂ and suggestthat quaternary combinations are possible.

Despite these advances, there is still a need for a new generation ofcathode-active compounds that can provide high capacity with low cost,good cycleability, and high stability, particularly at voltage levelsabove about 4.2 volts. There is also a need for methodologies forpreparing homogeneously mixed multi-metallic compositions that caneffectively combine each metal's performance characteristics. Inaddition, there is a need to find such cathode-active compounds thatminimize the irreversible capacity loss during the first and subsequentdelithiation cycles and that have increased mid-point cell voltage. Itis to such needs that the present invention is directed.

SUMMARY OF THE INVENTION

Briefly, therefore, the present invention is directed to a novelpositive electrode-active material comprising a composite oxide in asingle phase having the general formula Li_(x)M1 _(y)M2 _(z)M3 _(u)M4_(w)O_(n), where 0<x≦2, the sum of y+z+u+w is about 1 to 2, y, u and ware each greater than 0, and 2≦n≦4, where M1, M2, M3 and M4 aredifferent and are selected from the group consisting of Ba, Mg, Ca, Sc,Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, N, P, As, Zr, Hf,Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, and whereone of M1, M2, M3 and M4 is present in an amount of at least about 70mol percent of the combined M1, M2, M3 and M4.

The present invention is also directed to a novel method of producing apositive electrode-active material comprising the steps of (a) mixingsalts of four different metals selected from the group consisting of Ba,Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, As,Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, intosolution in a liquid solvent; (b) precipitating a homogeneous mixture ofthe four metals from the solution; (c) adding lithium to the homogeneousprecipitated mixture; and (d) calcining the mixture of lithium and thefour different metals in the presence of oxygen to form a lithiatedcomposite oxide of the four metals.

The present invention is also directed to a novel electrochemical cellproduced by the method described just above, wherein0.7≦z/(y+z+u+w)<1.0.

The present invention is also directed to a novel electrochemical cellcomprising a positive electrode, a negative electrode and an electrolytewhich electrochemically interconnects the positive electrode and thenegative electrode, wherein the positive electrode comprises a compositeoxide in a single phase having the general formula Li_(x)M1 _(y)M2_(z)M3 _(u)M4 _(w)O_(n), where 0<x≦2, the sum of y+z+u+w is about 1 to2, and 2≦n≦4, where M1, M2, M3 and M4 are different and are selectedfrom the group consisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co,Cu, Zn, Al, B, Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os,Ir, Au, Sn, and lanthanides, and where one of M1, M2, M3 and M4 ispresent in an amount of at least about 70 mol percent of the combinedM1, M2, M3 and M4.

The present invention is also directed to a novel lithium-ion batterycomprising a sealable cell container, a positive electrode, a negativeelectrode, an electrolyte solution, a separator, a positive electrodecurrent collector, and a negative electrode current collector, where thepositive electrode comprises a composite oxide in a single phase havingthe general formula Li_(x)Mn_(y)Ni_(z) Co_(u)Al_(w) O_(n), where 0<x≦2,the sum of y+z+u+w is about 1 to 2, and 2≦n≦4, and 0.7≦z/(y+z+u+w)<1.0.

The present invention is also directed to a novel method of producing apositive electrode-active material that is a composite oxide of at leasttwo metals, the method comprising the steps: (a) forming a mixture ofthe hydroxides of at least two metals selected from the group consistingof Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge,As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides,where at least one of the metals is in its lowest oxidation state; (b)contacting the mixture with oxygen under conditions suitable for thefurther oxidation of at least some of the metal hydroxides; (c) addinglithium to the mixture; and (d) calcining the mixture in the presence ofoxygen to form a lithiated composite oxide of the at least two metals.

Among the several advantages found to be achieved by the presentinvention, therefore, may be noted the provision of cathode-activecompounds that provides high capacity with low cost, good cycleability,and high stability—at voltage levels above about 4.2 volts; theprovision of methods for preparing homogeneously mixed multi-metalliccompositions that can effectively combine each metal's performancecharacteristics; the provision of such cathode-active compounds thatminimize the irreversible capacity loss during the first and subsequentdelithiation cycles and that have increased mid-point cell voltage.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart illustrating the production of quaternary cathodematerials by a co-precipitation process;

FIG. 2 is a flow chart illustrating the production of quaternary cathodematerials by co-precipitation followed by a freeze drying process;

FIG. 3 is an illustration of a lithium-ion cell as an embodiment of thepresent invention;

FIG. 4 is a graph showing the x-ray diffraction pattern of a sample ofLiNi_(0.7)Mn_(0.2)Co_(0.05)Al_(0.05)O₂ sintered at 750° C. for 24 hours;

FIG. 5 is a graph showing the charge/discharge profile ofLiNi_(0.7)Mn_(0.2)Co_(0.05)Al_(0.05)O₂ in a solution lithium-ion cellwith lithium metal foil as an anode;

FIG. 6 is a flow chart showing the preparation of quaternary cathodematerials by co-precipitation followed by a slow oxidation process;

FIG. 7 is a graph showing the x-ray diffraction pattern of a sample ofLiNi_(0.25)Mn_(0.7)Co_(0.025)Al_(0.025)O₂ sintered at 750° C. for 24hours;

FIG. 8 is a graph showing the charge/discharge profile of a solutionlithium-ion cell having LiMn_(0.7)Ni_(0.25)Co_(0.025)AL_(0.025)O₂ as apositive electrode-active material using cut-off voltages of 4.2, 4.6and 4.8 volts;

FIG. 9 is a graph showing the charge/discharge capacity of a cell havingLiMn_(0.7)Ni_(0.25)Co_(0.025)AL_(0.025)O₂ as a positive electrode-activematerial in its first 12 cycles between 1.5-5 volts; and

FIG. 10 is a graph showing voltage as a function of time for the first12 charge/discharge cycles between 1.5-5 volts of a cell havingLiMn_(0.7)Ni_(0.25)Co_(0.025)AL_(0.025)O₂ as a positive electrode-activematerial.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Reference now will be made in detail to the embodiments of theinvention, one or more examples of which are set forth below. Eachexample is provided by way of explanation of the invention, notlimitation of the invention. In fact, it will be apparent to thoseskilled in the art that various modifications and variations can be madein the present invention without departing from the scope or spirit ofthe invention. For instance, features illustrated or described as partof one embodiment, can be used on another embodiment to yield a stillfurther embodiment.

Thus, it is intended that the present invention cover such modificationsand variations as come within the scope of the appended claims and theirequivalents. Other objects, features and aspects of the presentinvention are disclosed in or are obvious from the following detaileddescription. It is to be understood by one of ordinary skill in the artthat the present discussion is a description of exemplary embodimentsonly, and is not intended as limiting the broader aspects of the presentinvention.

In accordance with the present invention, it has been discovered thatnew quaternary composite oxide materials can be produced that providesuperior properties when used as positive electrode-active materials inlithium-based secondary batteries. The scope of the materials isgenerally formulated as Li_(x)M1 _(y)M2 _(z)M3 _(u)M4 _(w)O_(n), whereM1, M2, M3, and M4 are cationic metal components of the composite oxideand are selected from different metal elements that are described indetail below. For the purposes of the formulated material, the range ofx can vary from 0 to 2 and the sum of y+z+u+w is about 1 to 2. The rangeof the oxygen can vary from 2 to 4. A key feature of the new materialsis that one of the metals that form the composite oxide—namely, M1, M2,M3 and M4 —is present in an amount of at least about 70 mol percent ofthe combined amount of the four metals. In certain embodiments, theoxides may be either nickel-rich, or manganese-rich. As used herein, thecomposite oxide is referred to as being “nickel-rich” if nickel forms atleast about 70 mol percent of the combined amounts of M1, M2, M3 and M4,and as “manganese-rich” if manganese forms at least about 70 mol percentof such metals.

The subject composite oxides may be a simple composite mixture of eachindividual metal oxide. It is believed that although the composite heremay be considered as homogeneous physically, the performance relies uponthe discrete particles of each metal oxide. These materials may be madeto have a homogeneous structure on a molecular level. For the purposesof this application, the term “homogeneous” shall mean that thematerials made from different metal components exist, in at least amajor part, in a single-phase morphology in which the distribution ofeach metal element is ideally defined by unit cells of the crystalstructure. The subject oxides may be substantially completely singlephase. The performance of the material thus does not depend on eachindividual component, rather it depends upon the combining of theperformance characteristics of all components.

It is believed that the composite oxide materials of the currentinvention have a unique structural arrangement that facilitates thetransportation of lithium ions during charge/discharge. The structuralarrangements may be amorphous, layered, spinel, shear, or other,according to the oxide composition. Compositions that are cobalt- andnickel-rich (>70 mol %) may have layered structures, while compositionsthat are manganese-rich (about 70 mol %, and above) may possess a spinelstructure.

It is desirable that the present composite oxides combine the preferredcharacteristics of each metal element. Factors to consider in designingsuch a system include one or more of the following: capacity,electrochemical stability, thermal stability, conductivity, density,availability, cost, toxicity, preparation, morphology, bonding,homogeneity safety, thermal stability, voltage, current density, andmoisture stability. For example, one component may have betterelectrochemical stability while another may have better thermalstability. One metal may provide a flat discharge profile (for exampleLiCoO₂) while another may show a twostage discharge profile (for exampleLiMn₂O₄).

Positive electrodes that have been produced with the new quaternarycomposite oxides have shown superior properties when compared withelectrodes using conventional electrode materials. For example,manganese-rich quaternary oxides surprisingly have demonstrated stablecharge/discharge cycling at over 4.2 volts, in fact at over 4.6 voltsand over 4.8 volts, with some materials showing stability at up to 5.0volts, compared with a normal limit of about 4.2 volts with conventionalmaterials, such as LiCoO₂.

The subject quaternary composite oxides have the general formula:

Li_(x)M1 _(y)M2 _(z)M3 _(u)M4 _(w)O_(n)  (1)

where x is equal to or between 0 and 2, n is equal to or between 2 and4, the sum of y, z, u and w is equal to or between 1 and 2, and each oneof y, z, u and w is always greater than zero. These relationships canalso be expressed as, respectively, 0≦x≦2, 2≦n≦4, 1≦(y+z+u+w)≦2, and y,z, u and w are each >0. As used herein, the symbol (≦) is to be taken tomean “is equal to or less than”, and the symbol (≧) is to be taken tomean “is equal to or more than”. Likewise, the symbol (<) is to be takento mean “is less than” and the symbol (>) is to be taken to mean “ismore than”. In each one of the subject composite oxides, one of the M1,M2, M3 and M4 components is present in an amount that is at least about70 mol percent of the combined amount of M1, M2, M3 and M4. This can beexpressed, for example, as 0.7≦y/(y+z+u+w)<1.0, for the case where M1 isthe component that is present at a level above 70 mol percent, and as0.7≦z/(y+z+u+w)<1.0, for the case where M2 is the component that ispresent at a level above 70 mol percent.

As used herein, the term “quaternary composite oxide” means a compositeoxide having four different cationic metal components that are in theform of oxides. For example, the subject composite oxides having thegeneral formula: Li_(x)M1 _(y)M2 _(u)M3 _(u)M4 _(w)O_(n), are suchquaternary composite oxides, where the M1, M2, M3 and M4 components arethe four different cationic metal components of oxides that form thelithium insertion compound, or lithium intercalation compound thatreversibly accepts and donates lithium (Li) atoms. As used herein,“lithium insertion compound”, and “lithium intercalation compound” bothmean a compound composed of a crystalline lattice that acts as anelectron donor and foreign electron acceptor by donating or acceptinglithium atoms that are interspersed or diffused between the planes ofthe lattice. In such a reaction, the structure of the host is changedonly by atomic displacements and the reaction does not involve adiffusive rearrangement of the host atoms. The guest species may beneutral, an electron donor, or an electron acceptor. More specifically,an intercalation compound, as that term is used in the presentspecification, refers to compounds in which lithium-ion can betopotactically and reversibly inserted/extracted over a finite range ofsolid solution.

In the present quaternary composite oxides, the components M1, M2, M3and M4 are each different from the other and are selected from the groupconsisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B,Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, andlanthanides. In particular, M1, M2, M3 and M4 may be selected from thegroup consisting of Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, Ga, Zr, Hf,Mg, Ca, and Sn, and, in certain instances, M1 is manganese, M2 isnickel, M3 is cobalt and M4 is aluminum.

Accordingly, the general formula for a certain form of the subjectuaternary composite oxides is:

Li_(x)Mn_(y)Ni_(z)Co_(u)Al_(w)O_(n)  (2)

where: 0≦x≦2,2≦n≦4,1≦(y+z+u+w)≦2,y, z, u and w are each >0, and one ofMn, Ni, Co and Al is present at a level of at least about 70 mol percentof the combined amount of Mn, Ni, Co and Al. In certain embodiments,either Mn or Ni will be present at a level of at least about 70 molpercent of the combined amount of Mn, Ni, Co and Al, and, in otherembodiments, Mn will be present at a level of at least about 70 molpercent of the combined amount of Mn, Ni, Co and Al (i.e.,0.7≦y/(y+z+u+w)<1.0).

The variation of x (i.e., the relative amount of lithium in thelithiated oxide) can be controlled either by an electrochemical redoxprocess or by the stoichiometry of the chemical synthesis. Theelectrochemical redox process may entail the use of lithium metal, theuse of a lithium-ion containing reducing agent such as LiBu, LiAlH₄, orLi-superhydride, or the use of a lithium intercalation compound. Controlof the amount of lithium by chemical synthesis refers to one of thefollowing processes carried out with a lithium-ion containing agent:thermal dehydration, thermal decarbonylation, thermal decomposition, ionexchange, sol-gel process, co-precipitation, and similar processes thatare well known in the art.

The quaternary composite oxides can be produced by mixing sources of theM1, M2, M3 and M4 metals in the desired relative amounts, adding lithiumto the mixture, and calcining the mixture of lithium and M1-M4 in thepresence of oxygen to form a lithiated composite oxide material havingthe general formula shown in formula (1), above.

One method of synthesizing the quaternary composite metal oxides is bysimply intermixing the hydroxides of each of the four metals. Theintermixed metal hydroxides can then be calcined in the presence ofoxygen, usually at temperatures over about 500° C., to form a compositeoxide. However, if solid forms of the metal hydroxides are used, thismethod generally requires lengthy reaction time and high temperatures asthe reaction proceeds by diffusion of each component to the othercomponents. Also the morphology of the resulting material will bedifficult to retain in a single phase.

An alternative method of synthesis involves a solution sol-gel process.A sol-gel process refers to a process that includes a wet chemicalmethod and a multistep process involving both chemical and physicalprocesses such as hydrolysis, polymerization, drying, and densification.The transition of a liquid sol containing all desired metal componentsto a solid allows for the production of homogeneous materials in a widevariety of forms. Starting materials in the preparation of the solinclude inorganic salts or organometallic compounds such as alkoxides.One preparation process is first to make a solution sol by a series ofhydrolysis and polymerization reactions to form a colloidal suspension,and then convert the sol into a gel. In the final stage, the gel isconverted into dense cathode-active compounds after heat treatment.Inorganic salts and organometallic compounds for sol-gel processes maybe selected from one or more of following: nitrates, sulfates,phosphates, halides, alkoxides, and polymeric organometallicoxoalkoxides.

In the present invention, it has been found that a way to makehomogeneously mixed material is to start at the beginning of thematerial preparation process. A salt of each of the four metalcomponents is placed into solution in a solvent in an amount (relativeto the amount of the other three metals) that is proportional to theamount of the metal that is desired for the final quaternary compositeoxide. The metals can then be co-precipitated from the solution to forma homogeneous mixture that contains the desired amount of eachcomponent. The precipitation can be carried out by the addition of achemical that converts the soluble salt forms of each component intoforms that are insoluble in the solvent. This can be illustrated in thefollowing Equation 3, where nitrates of each of the four metals in watersolution are converted into metal hydroxides, which are insoluble underthe same conditions, by the addition of a hydroxide.

When the salts of the four metals are placed into solution in a solvent,it is believed that any liquid can be used as the solvent. For example,the liquid may be one in which the low-covalent salts of each of thefour metals are soluble. When it is said that a salt is “soluble” in asolvent, what is meant is that the salt is soluble in the solvent at 20°C. in an amount of at least about 10 g/l, preferably at least about 50g/l, more preferably at least about 100 g/l, and yet more preferably atleast about 200 g/l. Water, alcohols, and volatile ketones andaldehydes, and mixtures of these are suitable solvents.

As mentioned above, the co-precipitation of the metals to form ahomogeneous mixture can be carried out by any method. Although theaddition of a chemical to convert soluble metal salts into insolubleforms (for example, into hydroxides when an aqueous solution is used) isa common method for precipitation, the use of temperature, phase change,and any other method that results in the formation of a homogeneoussolid mixture of the metals can be used.

When a homogeneous mixture of the desired components of the compositeoxide is obtained, a method for converting it to the oxide form is by acalcination step. Often the calcination step is the longest andenergy-consuming step in the process for producing a composite oxide.Depending on the starting materials, the calcination step will lead to:(a) dehydration of the hydrides, decarbonylation of the carbonates; (b)oxidation of each metal element to a desired oxidation state; and (c)formation of the crystal structure of the material. In some cases,calcination may only lead to amorphous materials.

In quaternary systems, it is believed that it is difficult to prepare asingle-phase composite oxide because of the tendency of quaternarysystems to phase separate during either the lithiation step or duringcalcination. Compared with direct solid state synthesis, for example,the inventors have found that solution processes such asco-precipitation and gel formation by sol-gel methods are capable ofproviding materials that can be more tightly controlled duringlithiation and calcination and consequently provide composite oxideshaving more tightly controlled final structure.

Surprisingly, the inventors have found that when oxygen is used to causean interconnection between and among the M1-M4 metals before lithiation,the tendency of the mixture to phase-separate is significantly reduced.This oxidation may generally take place at a relatively low temperature,below about 120° C., for example. It is believed that when thehomogeneous mixture of the M1-M4 hydroxides, after precipitation, iscontacted with oxygen under conditions designed to provide that at leastsome of the hydroxides are further oxidized, the three-dimensionalstructure of the mixture is stabilized to a degree sufficient to largelyprevent phase separation during lithiation and calcination. Lithiationcan then take place after such partial oxidation. One method tofacilitate this low temperature oxidation is by the use of low covalentmetal ions as the precursors for the solution process. As used herein,the terms “low covalent”, “lowest oxidation state” and “low valenceform”, when used to describe the oxidation state of a metal ion, areintended to have the same meaning. The low covalent ions are believed topermit the acceleration of the oxidation of the precursors at lowertemperatures than normally required, and thereby to reduce subsequentphase separation. It is well-known that manganese has various oxidationstates. The main oxidation states of manganese are +2, +3, +4, +6, +7.This is determined by the electronic configuration of managese, 3d⁵4s²,in which all seven electrons can be removed.

Because of its ability to form different oxidation states, manganeseoxides are also diverse. Depending on acidic or basic conditions, theseoxides can exist as different forms. Various metal oxides and theirrelationship versus their redox potential are described by D. F. Shriveret al., in Inorganic Chemistry, W. H. Freeman and Company, p. 654,(1990). That reference describes the redox potential for manganeseoxides at various acidic and basic pH values in terms of the diagramsshown below. The upper diagram shows acidic conditions and the bottomdiagram shows basic conditions.

From consideration of the redox potential under basic conditions, theoxidation of low-covalent Mn(II) to Mn(IV) is much easier. Since thepotential of MnO₂/Mn(OH)₂ couple, E^(o) MnO₂/Mn(OH)₂=−0.05V, is lowerthan that of O₂/OH—couple, E^(o)=0.401V, Mn(OH)₂ can be easily oxidizedthan, for example, Mn(OH)₄, by molecular oxygen in air to form oxocompounds, as follows:

Mn(II)+2OH—→Mn(OH)₂↓white precipitate  (4)

Mn(OH)₂+O₂ΔMn(O₂)(OH)₂→MnO(OH)₂ brown precipitate  (5)

The ease of oxidation of low covalent manganese compounds is believed tobe important for the current invention. The relative ease of theintroduction of oxygen into manganese-rich materials in air at ambienttemperature is believed to provide a significant advantage to fix thematerial structure through oxygen bridges.

Besides Manganese, other low covalent metal ions such as Co(II), Ni(II),Cr(Iii), Fe(II), Cu(I) and others are known that have a strong tendencyto react with oxygen at low temperatures to form a variety of oxygencompounds. Thus, it is believed that the multi-metallic mixturescontaining at least one low covalent metal are particularly useful.Therefore, low covalent metal ions such as Mn(+2), Co(+2), Ni(+2),Cr(+3), Fe(+2), Cu(+1), as opposed to the higher oxidation states ofeach of these elements may be preferred.

Without being bound to this, or any other particular theory, theinventors believe that the use of salts having the low-valence forms ofthe four metal cations results in the formation of a composite oxideprecursor material that can be oxidized at relatively low temperaturesto stabilize the three-dimensional structure of the composite with theresult being that when the mixture is lithiated and calcined, a finalquaternary composite oxide having only a single phase is produced. Atleast one of the metal salts may comprise the metal in its lowestoxidation state. In other embodiments, at least two, at least three, orall four of the metal salts may comprise the metals in their lowestoxidation states. A particular mixture of salts, therefore, includessalts of Mn(+2), Ni(+2), Co(+2) and Al(+3).

A method by which this low-temperature oxidation can be carried out isto co-precipitate the metals as hydroxides and to separate theprecipitated homogeneous mixture from the liquid solution, and then toheat the mixture in the presence of air to a temperature of betweenabout 40° C. and about 120° C. for a period sufficient for at least someof the hydroxides to be further oxidized. When it is said that “at leastsome” of the hydroxides are further oxidized, it is meant that anyfraction of the hydroxides that are present in the mixture are furtheroxidized according to the type of reaction shown in equation (5). Atleast about 1% of the hydroxides, in some cases at least about 5%, and,in other cases, at least about 10% of the hydroxides may be furtheroxidized. In order to facilitate this reaction, the mixture may beheated in air at a temperature of between about 60° C. and about 100° C.for a period of from about 1 day to about 8 days or, alternatively, at atemperature of about 80° C. for a period of from about 1 day to about 5days. It is desirable that the temperature that is used for this step below enough to avoid phase separation of the precipitated mixture.

An alternative process for low-temperature oxidation is to contact themetal hydroxides with oxygen while the hydroxides are still in the formof a suspension in the solvent. In this instance, air, oxygen gas, orany other form of, or source of oxygen can be used to supply the oxygen.A common method would be to bubble air through the suspension at atemperature of from about room temperature to about 100° C. Anothermethod would be to contact the hydroxides with a source of oxygen insolution form, for example, by the addition of peroxides to thesolution. Aqueous hydroperoxides could be the source of the oxygen andcould be added to the solution during or after the precipitation step.It is believed that advantages of this method of oxidation may be thatthe oxidation reaction can be more precisely controlled by controllingthe type, amount, and concentration of such peroxides that are added, bycontrolling the temperature of the solution, and with the result beingthat uniform oxidation of the hydroxides is obtained.

Another aspect of the preparation method is the addition of lithiumafter precipitation and, typically, after the low temperature oxidation.In the case of a co-precipitation process from an aqueous solution, itis not known to be possible to directly co-precipitate a Li ion into themixture. In such cases, the co-precipitation of other metal componentscan be obtained in a first step and a lithium ion source can be added tothe homogeneous precipitated mixture in a subsequent step. The lithiumion source may be one of the following compounds: Li₂CO₃, LiOH, LiNO₃,LiPO₄, LIF, LiCl, LiI, LiOH·H₂O, Li₂SO₂, LiOAc. The source of lithiummay be hydrated LiOH, since the water molecules are believed tofacilitate the binding and diffusion of the lithium ions into thematerial. For certain compositions of the subject quaternary compositeoxides, namely in manganese-rich oxides, it is also possible that if oneof the desired components does not have a suitable precursor for theinitial co-precipitation, the same principle of adding lithium ions canbe used to add such components in a subsequent step together with alithium source.

A particular process for the production of the subject quaternarycomposite oxides by co-precipitation from solution is illustrated inFIG. 1. As shown, metal nitrates are used as the metal salts that areused to form a solution in water. LiOH is added as a base to cause theco-precipitation of metal hydroxides. If desired, oxidation of thehomogeneous precipitated mixture can then carried out as described aboveto further oxidize the metal hydroxides. Lithium is added, and themixture is calcined to form the final lithiated quaternary compositeoxide.

The use of the low-temperature oxidation step as a method to avoid phaseseparation during lithiation and/or calcination has been described abovein the context of the preparation of the quaternary composite oxides ofthe present invention. However, it is believed that this method can beused advantageously for the preparation of any composite oxide materialhaving at least two metal components. Thus, the preparation of binaryand ternary, as well as quaternary composite oxides would benefit fromthe application of this step.

A modification to the production process is the addition of afreeze-drying, or lyophilization, step between the precipitation and thecalcination. PCT Patent Application WO 98/16900 discloses afreeze-drying process in the preparation of aluminum-doped lithiumcobalt oxide. For the present quaternary systems, the freeze-dryingprocess is believed to be useful in effectuating the homogeneousdistribution of lithium-ions in the precursor mixture beforecalcination. A schematic flow sheet of a production process thatincorporates a freeze-drying step is shown in FIG. 2. In this method, alithium source is added to the homogeneous precipitate. Lithium sourcesinclude the water-soluble lithium-containing compounds Li₂CO₃, LiOH,Li₂SO₄, LiNO₃, Li₃PO₄, LiF, LiCl, and LiI. An aqueous suspension of thehomogeneous precipitate and the added lithium is separated intodroplets, such as by spraying, and the droplets are frozen. One methodfor preparing such frozen droplets is to spray the suspension into afluid, such as liquid nitrogen, that is at a temperature below 32° F.After the frozen droplets are recovered from the freezing medium, theyare subjected to drying under vacuum, so that the water sublimes fromthe droplets, leaving a dry mixture of lithium hydroxide and thehydroxides of nickel, manganese, cobalt and aluminum. If desired, thedried droplets can be milled to a powder prior to being calcined intothe final composite oxide.

After the low-temperature oxidation, if it is used, or prior to thefreeze-drying step, lithium can be added to the mixture. The amount oflithium that may be added is within a range of about 0.9 to about 1.1 ofthe combined amounts of the nickel, manganese, cobalt and aluminum, on amolar basis. Any of the previously mentioned sources of lithium can beused for this step, and the lithium may be well mixed into the oxidizedmixture prior to calcination, or added to the solution prior to itsfreeze-drying. Lithium hydroxide may be the source of lithium. After theaddition of lithium, the mixture can be calcined as described above.

Another aspect of the current invention is the structure of the materialproduced. It is expected that the crystal structure of a givenquaternary material may not resemble that of any compound based on asingle metal. This will be particularly true if each component in thematerial has close ratios, such as, 1:1:1:1. However, a quaternarymaterial may still adopt a structure that is similar to a single metalcompound in the case where one of the components is the major part ofthe composition. Structures particularly suitable for the currentinvention are ones that are able to facilitate the transportation oflithium ions with very low irreversible capacity loss and withoutcollapse of the structure during lithium-ion intercalation.

In certain embodiments, the quaternary composite oxides of the presentinvention may have only a single phase. In the case of nickel-richmaterials, the single phase may be a typical layered structure, while inthe manganese-rich materials, the single phase may be a typical be aspinel structure. However, it should be noted that the assignment ofprecise structure to quaternary systems is somewhat arbitrary due to thenature of the systems in solid form.

The positive electrode-active materials of this invention can be used inany application or manner that any conventional positiveelectrode-active material is used. One use of the new materials is forthe production of cathodes for use in electrochemical cells. In atypical electrochemical cell, key components are a positive electrode, anegative electrode, and an electrolyte which electrochemicallyinterconnects the positive electrode and the negative electrode. It isoften desirable for the positive and negative electrodes to be isolatedfrom each other by a separator.

For the production of positive electrodes of the present invention, thesubject quaternary composite oxide material can be mixed with a binderand a conductive material, such as carbon black, and the mixture isformed into an electrode. A specific example is to mix 200 parts byweight of the quaternary composite oxide with 100 parts of binderpolyvinyldifluoride (PVDF 2801 and 2751, available from Elf Atochem,Philadelphia, Pa.), and 30 parts of acetylene carbon black (availablefrom Alfa Aesar Chemical, Ward Hill, Mass.), and to mix these materialsin a SPEX ball-mill mixer (available from Spex CertiPrep, Metuchen,N.J.) until they are homogeneously intermixed. The mixed material isthen removed from the mill and pressed into a pellet. The pelletelectrode is then dried under vacuum at a temperature of from about 60°C. to about 140° C. for at least about 12 hours before testing. Variousshapes of electrodes include squares, rectangles, bars and circles, butelectrodes can be of any desired shape.

Negative electrodes (or anodes) for use in the current invention includelithium metal and lithium intercalation compounds. A particular anodeuseful in the present invention is thin lithium metal foil, commerciallyavailable from Aldrich, Fisher, and Strem. A lithium intercalationcompound for use as an anode may be one of the following materials:natural graphite, synthetic graphite, non-graphite carbon materials, andlithium tin oxides. Such intercalation compounds are typically purenatural or synthetic graphites that can be purchased from variouscommercial sources such as Aldrich.

Various non-aqueous organic solvents and lithium containing salts can beused to create a suitable electrolyte composition in the currentinvention. Non-aqueous organic solvents include one or more of thefollowing: propylene carbonate (PC), ethylene carbonate (EC), dimethylcarbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC),tetrohydrofuran (THF), methyl tetrohydrofuran (MTHF), dimethyltetrohydrofuran (DMTHF), diethyl ether (DE), acetonitrile, and anycombinations containing one or more solvents listed above. Lithium saltsinclude LiPF₆, LiBF₄, LiClO₄, LiCl, LiF, LiI, LiSO₃CF₃, LiSO₃CMe,LiB(C₆H₅)₄, LiN(SO₂CF₃)₂, and LiAsF₆. The electrolyte combination may beprepared as one of the following: a solvent from the above list and alithium salt listed above; a binary mixture of two solvents and alithium salt; a ternary or higher mixture of three or higher solventsand a lithium salt; a mixture of at least two solvents and at least twolithium salts. In certain embodiments, an electrolyte solution may becomposed of LiPF₆ in a mixture of PC and EC, or PC and EMC, or PC, EC,and DMC. The lithium salt solution may be in the range of 0.5 M to 4.0M, with a particular range being about 1 M to about 3 M, and anotherparticular range being about 2.5 M. Particular electrolyte compositionsmay be 1 M or 2.5 M LiPF₆ solution in 1:1 propylene carbonate (PC) andethylene carbonate (EC).

Separators used in the current invention may be various microporousmembranes. Microporous films useful in the present invention aretypically those that are electrochemically stable and will not decomposeduring cycling. Commercially available separators can be obtained fromHoechst Celanese of Dallas, known as Celgard 2300, Celgard 2400, andCelgard 2700. For use in the examples, separators were cut into desiredshapes, which are usually larger than both the cathode and anode, inorder to avoid the shortening of the cell.

The cathode materials that are a subject of the current invention aresuitable for lithium, lithium-ion, and lithium-ion polymer cells. Forthe purposes of this application, the term “lithium batteries” shallmean batteries that use lithium metal as an anode component while theterms “lithium-ion” and “lithium-ion polymer batteries” shall meanbatteries that use lithium insertion compounds as anode components. Theterm “lithium-based batteries” shall refer to all three types ofbatteries.

As shown in FIG. 3, a lithium-based battery 10 (regardless of actualbattery type) is composed of an anode 20 (lithium foil for lithium cell,an intercalation compound for lithium-ion and lithium-ion polymercells); an electrolyte 30 (a lithium salt solution and a separator forsolution cells and a gel electrolyte containing lithium salt solutionfor polymer cells); a cathode 40; current collectors for both electrodes50 and 60; and a sealable cell container 70. The construction of suchbatteries is well known in the art and is described, among other places,in U.S. Pat. Nos. 5,370,948, 5,804,335, 5,792,574, 5,626,635, 5,609,975,5,599,642, 5,514,496 and 5,490,320.

A lithium-ion battery generally includes a sealable cell container, apositive electrode, a negative electrode, an electrolyte solution, aseparator, a positive electrode current collector, and a negativeelectrode current collector. In the lithium-ion batteries of the presentinvention, the positive electrode comprises either a composite oxidehaving the general formula Li_(x)Mn_(y)Ni_(z)Co_(u)Al_(w)O_(n), where0<x≦2, the sum of y+z+u+w is about 1 to 2, and 2≦n≦4, and0.7≦y/(y+z+u+w)<1.0 (a manganese-rich cathode material), or a compositeoxide having the general formula Li_(x)Mn_(y)Ni_(z)Co_(u)Al_(w)O_(n),where 0<x≦2, the sum of y+z+u+w is about 1 to 2, and 2≦n≦4, and0.7≦z/(y+z+u+w)<1.0 (a nickel-rich cathode material). In either case,the composite oxide may be in a single phase.

When the lithium-based battery is a lithium-ion polymer battery, thesealable cell container, the positive electrode, the negative electrode,and the separator comprise flexible polymeric materials.

In order to test the performance characteristics of the subjectbatteries, test cells, of either coin cell or Hoshen HS design, wereconstructed by the general procedure of first placing a lithium metalanode and a separator in a sealable cell container, and the cell wasthen flooded with 1 M LiPF₆ PC and EC solution (1:1). The cathode wasnext placed on top of the separator and the entire assembly was thensealed within the cell container. In the case of HS testing cells,copper and aluminum were used as current collectors.

The following examples describe various embodiments of the invention.Other embodiments within the scope of the claims herein will be apparentto one skilled in the art from consideration of the specification orpractice of the invention as disclosed herein. It is intended that thespecification, together with the examples, be considered to be exemplaryonly, with the scope and spirit of the invention being indicated by theclaims which follow the examples.

GENERAL PROCEDURES

In the examples, all percentages are given on a weight basis unlessotherwise indicated. All material syntheses were conducted in air.Electrochemical cell fabrication was performed in a complete glove boxsystem featuring NEXUS ONE style technology with computer display andmonitoring of both moisture and oxygen levels (available from VacuumAtmospheres Company, Danvers, Mass.).

Solvents, such as acetone, hexane, ethylene carbonate (EC), propylenecarbonate (PC) and dimethylethylene carbonate (DMC) were obtained fromAldrich Chemical Co., and were used as received. 1M solutions of LiPF₆in 1:1 mixtures of either PC:EC or EC:DMC were freshly prepared in theglove box before cell fabrication.

Chemicals, such as manganese nitrate, nickel nitrate, cobalt nitrate,aluminum nitrate and lithium hydroxide were obtained from AldrichChemical Co., and were used as received. Polyvinyl difluoride (PVDF)2801 and 2751 were obtained from Elf Atochem. Electrochemical gradeLiCoO₂ and LiMn₂O₄ were obtained from Aldrich Chemical Co., and wereused as received.

Cell charge/discharge testing was carried out using a Maccor batterytester (Series 4000, available from Maccor Inc, Tulsa, Okla). Rate ofcharge/discharge current was estimated based on the weight of activematerial in the cathode, depending on the size and surface area for eachindividual cell. The cell voltage range was determined by charging thecut-off voltages at 4.2, 4.4, 4.6, 4.8 and 5.0 volts. The cellperformance was calibrated with a known commercial cathode material(LiCoO₂), obtained from FMC Corporation.

EXAMPLE 1

This illustrates the production of quaternary cathode materials.

The procedure to make quaternary cathode materials comprises thefollowing steps: (a) making a quaternary mixture solution of desiredmetal nitrates in water; (b) adding LiOH solution to the abovequaternary nitrate mixture solution to effect the homogeneousco-precipitation of the respective metal hydroxides; (c) washing theprecipitate to eliminate lithium nitrates; (d) drying the hydroxidemixture; (e) grinding the dry hydroxide mixture and addingstoichiometric amounts of LiOH; and (f) calcining the solid mixture athigh temperature to afford lithiated quaternary metal oxide powder.

In a specific embodiment of the above procedure, a 100 ml of quaternarynitrate solution was prepared by mixing 1 M solutions of nickel nitrate,manganese nitrate, cobalt nitrate, and aluminum nitrate in a volumetricratio of 70:20:5:5 at room temperature with constant stirring. Theobtained solution was then treated with dropwise addition of 1.05 eq. Of1 M LiOH aqueous solution under stirring for about 2 hrs. The resultingprecipitate was separated from the aqueous solution by using acentrifuge and washed two times with water and separated each time inthe centrifuge. For purposes of the examples, the centrifuge consistedof an IEC clinical centrifuge from the International Equipment Co., ofNeedham Heights, Mass. The speed setting on the centrifuge was setbetween 3-5. The washed mixture was then placed in an oven at 80° C. toremove water. For the purposes of the examples the oven consisted of aconstant temperature oven Model DK-62, from American ScientificProducts. The dried powder was then mixed with 1.05 eq. Solid LiOH·H₂Oand mixed by a SPEX ball-mill mixer (Spex CertiPrep, Metuchen, N.J.) for30 mins. The material was next transferred into a porcelain crucible andcalcined at 750° C. for 24 hrs in air. For purposes of the examples, thefurnace was an Isotemp Programmable Muffle Furnace from FisherScientific. The calcined material was ground again by a SPEX ball-millmixer for 30 mins and re-calcined at 750° C. for 24 hrs in air. Thecalcined powder showed a black color.

In this regard, FIG. 4 shows the x-ray diffraction pattern of a sampleof the powder calcined at 750° C. for 24 hrs. The longer calcinationtime does not affect the diffraction pattern, with only minor changes onthe diffraction intensity. Compared to pure LiNiO₂ and other mixednickel containing systems, the x-ray diffraction pattern in thisinvention reveals the existence of a single-phase material. The analysisof the diffraction pattern under hexagonal setting furnishes latticeconstants to be a=2.487 and c=14.3425 Å, respectively. It should benoted that the structural assignment for this system as a layeredstructure is arbitrary because of the nature of dealing with quaternarysystems in a crystalline state.

EXAMPLE 2

This illustrates the preparation of cathode materials involving afreeze-drying process

The procedure to make quaternary cathode materials comprises thefollowing steps: (a) making a quaternary mixture solution of desiredmetal nitrates in water; (b) adding LiOH solution to the abovequaternary nitrate mixture solution to effect the homogeneousco-precipitation of the respective metal hydroxides; (c) washing theprecipitate to eliminate lithium nitrates; (d) mixing the precipitatewith a LiOH aqueous solution to make a homogeneous slurry; (e) addingthe slurry into liquid nitrogen to form frozen droplets; (f) drying thefrozen droplets under vacuum by a Labconco Lyophilizer system (LabconcoCorp., Kansas City, Mo.) to sublime the water; (g) grinding the drieddroplets to fine powders; (h) calcining the powder at desiredtemperature to afford lithiated quaternary metal oxide powder.

In a specific embodiment of the above procedure, a 100 ml of quaternarynitrate solution was prepared by mixing 1 M solutions of nickel nitrate,manganese nitrate, cobalt nitrate, and aluminum nitrate in a volumetricratio of 70:20:5:5. The obtained solution was then treated with thedropwise addition of 1.05 eq. of 1 M LiOH aqueous solution understirring for about 2 hrs to precipitate the metals as the respectivemetal hydroxides. The resulting precipitate was separated using acentrifuge and washed two times by water and separated each time in thecentrifuge. The washed mixture was then placed in a beaker and mixedwith 1.05 eq. of LiOH in 20 ml of water to afford slurry. The slurry wasnext freeze-dried by first forming droplets by adding the slurry intoliquid nitrogen to freeze the droplets. The frozen droplets wererecovered and dried at room temperature under full vacuum using a vacuumoven. For the purposes of the examples, the vacuum oven was a VacuthermVacuum Oven obtained from Kendro Laboratory Products of Germany. Thedried droplets were next ground in a SPEX ball-mill mixer for 5 mins andthen transferred into a porcelain crucible and calcined at 750° C. for24 hrs in air. The calcined material was ground again by a SPEXball-mill mixer for 30 mins and re-calcined at 750° C. for 24 hrs inair. The calcined powder showed a black color.

EXAMPLE 3

This illustrates a procedure for producing positive electrodes(cathodes) from the novel positive electrode-active material.

Positive electrodes in the current invention are prepared in two generalways. For solution cells, electrodes were made by a pellet process whilefor polymer cells, electrodes were fabricated by a film process.

Drying process: a mixture of 200 parts of cathode oxide (the materialmade as described in Examples 1 or 2, above), 100 parts of binderpolyvinylidene fluoride (PVDF) (Elf Atochem, Philadelphia, Pa.), and 30parts of acetylene carbon black (Alfa Aesar Chemical, Ward Hill, Mass.)were first prepared in a SPEX ball-mill mixer (Spex CertiPrep, Metuchen,N.J.) and then pressed into a pellet. The resulting pellet electrode wasthen dried under vacuum at a temperature range of 60° C. to 140° C. forat least 12 hrs before testing. Various shapes of the electrode includesquares, rectangular, and round. The thickness of the electrodes may befrom about 100 to 200 μm and the weight of the electrodes may be about10 ˜140 mg.

Wet process: a mixture of 100 parts of cathode oxide, 16 parts of binderPVDF, 5 parts of acetylene black, and 200 parts of acetone were firstprepared in a reaction vessel at 50° C. and then film was cast on aglass plate using a doctor blade. Upon drying of the solvent, theuniform film was easily removed from the glass plate and the electrodeswith desired sizes were obtained by use of a cutting board or a punch.The resulting electrodes were then dried under full vacuum at atemperature range of 60 to 140° C. for at least 12 hrs before testing.Shapes of the electrodes include square, rectangular, and round. Thethickness of the electrodes may be between 50 to 200 μm and the weightof the electrodes may be 10 ˜140 mg.

EXAMPLE 4

This illustrates a procedure for the production of negative electrodes.

The current invention uses both lithium metal and carbon anodes. Whenlithium negative electrodes (anodes) were required, lithium foil(Aldrich, thickness 0.75 mm) was cut into the desired shape and size andthen used directly in the cell.

When carbon anodes were required, they were produced by the followingprocedure:

Drying process: a mixture of 200 parts of graphite (Aldrich), 100 partsof binder PVDF (Alt Autochem, Philadelphia, Pa.), and 30 parts ofacetylene black were first prepared in a SPEX ball-mill mixer and thenpressed into a pellet. The resulting pellet electrode was then driedunder a vacuum at a temperature range of between 60° to 140° C. for atleast 12 hrs before the testing. The shapes of the electrodes includesquares, rectangular, and round. The thickness of the electrodes may befrom about 100 to 200 μm and the weight of the electrodes may be about10˜140 mg.

Wet process: a mixture of 100 parts of graphite, 16 parts of binderPVDF, 5 parts of acetylene black, and 200 parts of acetone was firstprepared in a reaction vessel at 50° C. and then film was cast on aglass plate using a doctor blade. Upon drying of the solvent, theuniform film was easily removed from the glass plate and the electrodeswith desired sizes were obtained by a cutting board or a punch. Theresulting electrodes were then dried under full vacuum at a temperaturerange of between 60° to 140° C. for at least 12 hrs before the testing.The shapes of the electrodes include square, rectangular, and round. Thethickness of the electrodes may be between about 50 to 200 μm and theweight of the electrodes may be about 10˜140 mg.

EXAMPLE 5

This example illustrates methods for the production of electrochemicalcells.

Solution cells: The solution testing cells in the current invention arefrom Hohsen Corp. (Japan) identified as HS testing cell. Testing typecells were constructed by the following procedures: The lithium metalanode and separator were placed on top of a copper-mesh currentcollector in the cell and then flooded with 1 M LiPF₆ PC and EC solution(1:1). The cathode was next placed on top of the separator and wasfollowed by an aluminum current collector. The cell was then sealed andtested on a Maccor battery tester (Maccor Inc., Tulsa, Okla.).

EXAMPLE 6

This example illustrates the electrochemical testing of theelectrochemical cells of the present invention.

Positive electrodes that were made from the compounds from Examples 1and 2 were tested in a Hohsen testing cell. The cells were charged anddischarged at constant current densities from 0.05 to 0.5 mA/cm² ofelectrode area using the battery tester.

FIG. 5 shows the charge/discharge profile for the solution cell with aquaternary Ni-rich cathode, prepared according to Example 1. Thecharging current was about 0.4 mÅ/cm² of the cathode electrode. Thecharging curve shows that the voltage was well above 4 volts, which ishigh when compared with single metal cathode materials made from nickel,cobalt, and manganese. The discharge voltage window was determined in anincremental manner to be between 1.5 to 5 volts using the batterytester. The capacities for charge and discharge for the first cycle werecalculated to be ˜200 and 164 mÅh/g, respectively.

The voltage of the Ni-rich cell reaches rapidly to the plateau above 4volts and then slowly goes up to 5 volts. The discharge reveals a welldefined sloping profile between 4.2 and 3 volts, which is different whencompared to other flat discharge profiles. The sloping discharge profileis the desired property for accessing the different discharge rateswithout the heating caused by internal resistance.

EXAMPLE 7

This example illustrates the production of a manganese-rich quaternarycomposite oxide positive electrode-active material including a slowoxidation step.

The procedure to make quaternary cathode materials comprises thefollowing steps: (a) making a quaternary mixture solution of desiredmetal nitrates in water; (b) adding LiOH solution to the abovequaternary nitrate mixture solution to effect the homogeneousco-precipitation of the respective metal hydroxides; (c) washing theprecipitate to eliminate lithium nitrates; (d) contacting the metalhydroxide precipitates with an oxygen source under conditions thatoxidation takes place; (e) mixing the oxidized precipitate with LiOH tointroduce the lithium source; and calcining the powder at desiredtemperature to afford lithiated quaternary metal oxide powder.

In a specific embodiment of the above procedure, a 100 ml of quaternarynitrate solution was prepared by mixing 1 M solutions of nickel nitrate,manganese nitrate, cobalt nitrate, and aluminum nitrate in a volumetricratio of 25:70:2.5:2.5. The obtained solution was then treated with thedropwise addition of 1.05 eq. of 1 M LiOH aqueous solution understirring for about 2 hrs to precipitate the metals as the respectivemetal hydroxides. The resulting precipitate was separated using acentrifuge and washed two times by water and separated each time in thecentrifuge. The resulting paste was then placed in an oven and slowlydried and oxidized at 80° C. for a period of from 1 to 5 days, dependingupon the composition. The dried powder was then mixed with about 1.1equivalents of LiOH·H₂O, transferred into a porcelain crucible, andcalcined at 750° C. for 24 hrs in air. The calcined powder showed abrown color.

An x-ray diffraction of this powder was obtained and is shown in FIG. 7.As can be seen from the figure, the material demonstrates a patterncharacteristic of a single-phase material.

EXAMPLE 8

This example illustrates the production of lithium-ion cells havingpositive electrodes that contained manganese-rich quaternary compositeoxide positive electrode-active material and shows the charge/dischargecapacity of those cells.

Several manganese-rich positive electrode-active materials havingdifferent compositions were produced by the method of Example 7.Positive electrodes for testing were made from each of the testmaterials by the method described in Example 3. Negative electrodes andlithium-ion test cells were produced by the methods described,respectively, in Examples 4 and 5. The lithium-ion test cells havingmanganese-rich quaternary oxides as cathodes were then tested foroperating voltage range and charge/discharge capacity over severalcycles as described in Example 6.

Determination of operating voltage range for the Mn-rich cathodematerials was the first step for performance evaluation. It was desiredto see if the Mn-rich materials had different characteristics than thetypical LiCoO₂, LiNiO₂ and LiMn₂O₄ electrodes, which are stable onlybetween about 2.5 to 4.2 volts. Accordingly, cells having a cathodecomprising the quaternary composite oxide that was produced in Example 7(Li Ni_(0.25)Mn_(0.7)Co_(0.025)Al_(0.025)O₂) were cycled in thefollowing voltage ranges: 1.5 to 4.2, 1.5 to 4.6, 1.5 to 4.8 and 1.5 to5.0. A representative plot of the charge/discharge profiles for thismaterial under different cut-off voltages is shown in FIG. 8.

As shown in FIG. 8, the manganese-rich material exhibits two chargeplateaus in the first cycle. The upper voltage limit for the firstplateau is about 4.6 volts. The discharge capacities are about 70 and120 mAh/g, respectively, when cells were cycled within voltage ranges of1.5-4.2 and 1.5-4.6 volts. However, the discharge capacity is almostdoubled to about 225 mAh/g when the voltage window is widened to 4.8volts. The flat second plateau between 4.6 to 4.8 volts is strikingbecause it highlights the difference between the Mn-rich quaternarysystems and present commercial cathode materials, such as LiCoO₂, LiNiO₂and LiMn₂O₄, which are unstable under these voltage conditions. Inconclusion, it was found that the Mn-rich cathode materials could becharged up to 5 volts.

The stability of the quaternary Mn-rich was tested by cycling a testcell having a cathode produced from material that was made according tothe method described in Example 7 through a number of charge/dischargecycles. FIG. 9 shows the charge and discharge capacities of the cell inits first 12 cycles between 1.5-5 volts. The initial drop of thecapacity in the first cycle is about 15%, which is comparable tocommercial cathode material LiCoO₂. However, there was no apparentcapacity decay after the first cycle. Actually, discharge capacitiesincreased slightly after the first cycle. In some testing cells,discharge capacities were found to be as high as about 260 mAh/g afterthe 4^(th) cycle.

A further evaluation of charge/discharge profiles is shown in FIG. 10,which shows the voltage as a function of the cycle. In the figure, asignificant difference can be seen between the first cycle andsubsequent cycles. Starting from the second cycle, the second plateauthat was observed between 4.6 and 4.8 volts is no longer visible,instead a smooth charge/discharge profile is seen. Without being limitedto this or any other particular theory, it is believed that such achange may indicate a structural transformation of cathode materialduring the first cycle.

In order to determine the effect of different levels of Mn, Ni, Co, andAl in the present quaternary composite oxide materials, cathodes wereproduced from several different composite oxides having the compositionsshown in Table 1.

TABLE 1 Composition and testing data for Mn-rich cathode materials.Weight Of Discharge Dishcarge Active Capacity; Capacity: SampleComposition Materials First cycle Fourth cycle No. (Mn:Ni:Co:Al) (mg)(mAh/g) (mAh/g) 1 70:25:2.5:2.5 27.3 222.6 254.9 2 70:20:5:5 26.1 228.0266.0 3 70:10:10:10 27.3 184.5 234.0 4 70:2.5:25:2.5 27.9 115.1 186.2 570:5:20:5 27.3 156.6 216.0 6 70:2.5:2.5:25 27.3 40.7 67.1 7 70:5:5:2029.1 64.3 93.9 8 80:10:5:5 27.9 156.0 227.8

As shown in Table 1, when manganese content is 70 mol percent of thecombination of Mn, Ni, Co, and Al, it was seen that higher Ni contentprovided higher capacities. For example, when Ni content is in the rangeof 20-25 mol percent of the quaternary oxide, the capacity of the cellwas highest.

The common feature for the Mn-rich cathode materials was their tendencyto give higher capacity after the first cycle, which is believed tounderscore the uniqueness of such materials. Generally, manganese-basedmaterials have shown the opposite trend upon cycling, which has longbeen a key obstacle for commercial applications. Moreover, the dischargecapacity of over about 200 mAh/g is rare for a manganese-based materialand is believed to represent significant progress in the formulation ofmanganese-based cathodes suitable for commercial use.

The performance of the Mn-rich cathodes was compared with theperformance of a commercial standard LiCoO₂ cathode under similartesting conditions. In voltage windows of 1.5-4.2, 1.5-4.6 and 1.5-4.8volts, discharge capacities for the standard LiCoO₂ cathodes were foundin the order of about 110, about 160, and about 170 mAh/g, respectively,in the first cycle. As expected, LiCoO₂ was stable in the 1.5-4.2voltage range, but degraded rapidly at higher voltages, especially inthe 1.5-4.8 volt range. For example, the discharge capacity of theLiCoO₂ cell was found to be about 140 mAh/g after the 3^(rd) cycle,which is a loss of about 30 mAh/g (or about 20%) from the value in thefirst cycle. The test showed that the Mn-rich quaternary compositeoxides had superior stability to LiCoO₂ oxides at higher voltages, andalso provided discharge capacities of over 200 mAh/g.

All references cited in this specification, including without limitationall papers, publications, patents, patent applications, presentations,texts, reports, manuscripts, brochures, books, internet postings,journal articles, periodicals, and the like, are hereby incorporated intheir entireties into this specification by reference. The discussion ofthe references herein is intended merely to summarize the assertionsmade by their authors and no admission is made that any referenceconstitutes prior art. Applicants reserve the right to challenge theaccuracy and pertinency of the cited references.

In view of the above, it will be seen that the several advantages of theinvention are achieved and other advantageous results obtained.

As various changes could be made in the above methods and compositionswithout departing from the scope of the invention, it is intended thatall matter contained in the above description and shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense. These and other modifications and variations to thepresent invention may be practiced by those of ordinary skill in theart, without departing from the spirit and scope of the presentinvention, which is more particularly set forth in the appended claims.In addition, it should be understood that aspects of the variousembodiments may be interchanged both in whole or in part. Furthermore,those of ordinary skill in the art will appreciate that the foregoingdescription is by way of example only, and is not intended to limit theinvention so further described in such appended claims. Therefore, thespirit and scope of the appended claims should not be limited to thedescription of the preferred versions contained therein.

What is claimed is:
 1. A positive electrode-active material comprising acomposite oxide having the general formula Li_(x) M1 _(y) M2 _(z) M3_(u) M4 _(w) O_(n), where 0<x≦2, the sum of y+z+u+w is about 1 to 2, y,z, u and w are each greater than 0, and 2≦n≦4, where M1, M2, M3 and M4are different and are selected from the group consisting of Ba, Mg, Ca,Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, N, P, As, Zr,Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, whereone of M1, M2, M3 and M4 is present in an amount of at least about 70mol percent of the combined M1, M2, M3 and M4, and which can be chargedat over 4.2 volts for a period of at least 3 hours when present in apositive electrode in an electrochemical cell.
 2. The material accordingto claim 1, wherein M1, M2, M3 and M4 are selected from the groupconsisting of Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, Ga, Zr, Hf, Mg, Ca,and Sn.
 3. The material according to claim 2, wherein M1 is manganese,M2 is nickel, M3 is cobalt and M4 is aluminum.
 4. The material accordingto claim 3, wherein 0.7≦z/(y+z+u+w)<1.0.
 5. The material according toclaim 4, wherein z/(y+z+u+w)>0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.1, andw/(y+z+u+w)≦0.1.
 6. The material according to claim 5, whereinz/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.05, andw/(y+z+u+w)≦0.05.
 7. The material according to claim 6, wherein thecomposite oxide has a general formula ofLi_(x)Mn_(0.2)Ni_(0.7)Co_(0.05)Al_(0.05)O_(n).
 8. The material accordingto claim 1, wherein the composite oxide is a single phase.
 9. Anelectrochemical cell comprising a positive electrode, a negativeelectrode and an electrolyte which electrochemically interconnects thepositive electrode and the negative electrode, wherein the positiveelectrode comprises a composite oxide having the general formula Li_(x)M1 _(y) M2 _(z) M3 _(u) M4 _(w) O_(n), where 0<x≦2, y, z, u and w areeach greater than 0, the sum of y+z+u+w is about 1 to 2, and 2≦n≦4,where M1, M2, M3 and M4 are different and are selected from the groupconsisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B,Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, andlanthanides, where one of M1, M2, M3 and M4 is present in an amount ofat least about 70 mol percent of the combined M1, M2, M3 and M4, andwhich can be charged at over 4.2 volts for a period of at least 3 hourswhen present in a positive electrode in an electrochemical cell.
 10. Theelectrochemical cell according to claim 9, wherein M1 is Mn, M2 is Ni,M3 is Co, M4 is Al, and 0.7≦z/(y+z+u+w)<1.0.
 11. The electrochemicalcell according to claim 10, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2,u/(y+z+u+w)≦0.1, and w/(y+z+u+w)≦0.1.
 12. The electrochemical cellaccording to claim 11, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2,u/(y+z+u+w)≦0.05, and w/(y+z+u+w)≦0.05.
 13. The cell according to claim9, wherein the composite oxide is a single phase.
 14. A lithium-ionbattery comprising a sealable cell container, a positive electrode, anegative electrode, an electrolyte solution, a separator, a positiveelectrode current collector, and a negative electrode current collector,where the positive electrode comprises a composite oxide having thegeneral formula Li_(x) Mn_(y) Ni_(z) Co_(u) Al_(w) O_(n), where 0<x≦2the sum of y+z+u+w is about 1 to 2, and 2≦n≦4, and 0.7≦z/(y+z+u+w)<1.0,and which can be charged at over 4.2 volts for a period of at least 3hours when present in a positive electrode in an electrochemical cell.15. The battery according to claim 14, wherein the positive electrode,the negative electrode, and the separator comprise flexible polymericmaterials.